UPTEC F 10021 Examensarbete 30 hp Juni 2015 X-Ray Photoemission Spectroscopy Characterization of Fe(II)- and Fe(III)-Phthalocyanine Molecular Films Sonja Droschke Abstract X-Ray Photoemission Spectroscopy Characterization of Fe(II)- and Fe(III)-Phthalocyanine Molecular Films Sonja Droschke Teknisk- naturvetenskaplig fakultet UTH-enheten This thesis investigates the electronic structure of iron phthalocyanine (Fe(II)Pc) and iron phthalocyanine chloride (Fe(III)PcCl) immobilized on surfaces. For this purpose Besöksadress: two different deposition methods are used and compared: smearing the molecular Ångströmlaboratoriet Lägerhyddsvägen 1 powder under atmosphere condition and evaporation of a molecular layer in Hus 4, Plan 0 ultra-high vacuum. The electronic states of FePc and FePcCl are probed with photoelectron spectroscopy (PES) and compared in relation to the ionic state of the Postadress: central metal (Fe). The PE spectra show that evaporation of FePcCl at around 350°C Box 536 751 21 Uppsala results in dissociation of the chlorine from the FePc molecule, which is stable at this temperature. Mass spectroscopic measurements during heating of FePcCl in ultra-high Telefon: vacuum (UHV) show a clear Cl signal for temperature still below 250°C. Theoretical 018 – 471 30 03 calculations of the binding energy for Cl in FePcCl seem to indicate dissociation of the Telefax: Cl from the molecules. 018 – 471 30 00 Hemsida: http://www.teknat.uu.se/student Handledare: Joachim Schiessling Ämnesgranskare: Carla Puglia Examinator: Tomas Nyberg ISSN: 1401-5757, UPTEC F 10021 1 Introduction ................................................................................. 4 2 Phthalocyanines .......................................................................... 5 3 Experimental set-up and technique ............................................. 6 3.1 Principles of photoelectron spectroscopy ................................................. 6 3.2 Chemical shift ............................................................................................. 7 3.3 Experimental equipment ............................................................................ 7 3.4 The evaporation chamber .......................................................................... 8 4 Sample preparation ................................................................... 10 4.1 Substrates ................................................................................................. 10 4.2 Deposition ................................................................................................ 10 4.3 Adsorbates................................................................................................ 11 4.3.1 Iron(II) phthalocyanine .................................................................. 11 4.3.2 Iron(III) phthalocyanine chloride ................................................... 12 5 Results and discussion of XPS data ............................................. 13 5.1 C 1s spectra .............................................................................................. 13 5.2 N 1s spectra .............................................................................................. 14 5.3 Fe 2p spectra ............................................................................................ 15 5.4 Cl 2p spectra ............................................................................................. 16 6 Results and Discussion of Mass Spectrometer Data ................... 19 7 Discussion .................................................................................. 24 8 Summary and Conclusions ......................................................... 28 9 Bibliography .............................................................................. 29 1 Introduction Nature has always been a source of inspiration when seeking for new technical solutions. Mankind’s attempt to imitate nature is nowadays called biomimetics1 (from the Greek words (life) and (to mime)). Already in the Greek mythology, Daidalos constructs “flying devices” by imitating bird wings to escape his prison. More recently, in 1948, the Swiss engineer George de Mestral invented the Hook and Loop fastener Velcro after studying annoying burrs. The investigation of lotus flowers led to the discovery of the lotus effect2 that made it possible to develop surfaces that can stay clean and dry themselves. Even this work is based on the aim to imitate nature, especially enzymes. Enzymes are organic macromolecules functioning as catalysts in biological processes. They are generally reaction-, substrate- and regio-specific making them highly efficient. They can run a reaction over and over again as they are left unaltered after the catalytic reaction. The disadvantage with enzymes is that they are sensitive to thermal and chemical changes in the surrounding. One group of catalysts used in biomimetics are porphyrins which are also found in the active site of many enzymes, as the two well-known examples of chlorophyll and haemoglobin. Purely artificial compounds called phthalocyanines (Pc’s) are built up in a structure similar to the natural porphyrins. However phthalocyanines showed to be very stable both chemical and thermal in contrast to porphyrins. Therefore phthalocyanines became of special interest for biomimetic applications. It is already common to use phthalocyanines in homogeneous catalysis (where the reactants and their products are in solution) for many industrial applications. Even though such homogenous processes are widely used, improvements are highly desired for increasing the lifetime of the catalysts and to overcome the difficulty to separate products from the catalysts. The immobilization of the catalytic molecules (Pc’s) on surfaces [1], (i.e. to use them in heterogeneous catalysis), has already shown to solve the separation problem and to improve the lifetime since the molecules, bonded on a surface, cannot form dimers or clusters which are the cause of the short lifetime of the homogeneous catalysis process. The aim of this work was to study the electronic structure of iron phthalocyanines deposited on surfaces in relation to the ionic state of the central metal (Fe). Therefore we have studied Fe(II)Pc and Fe(III) PcCl. Different deposition methods have been used and compared. Our results show that evaporation of FePcCl results in dissociation of the chlorine from the FePc molecule. 1 The term biomimetics was coined in the 1950s. Other words used for it are bionics, biomimicry and biognosis. 2 Discovered in 1997 by W. Barthlott and C. Neinhuis 4 2 Phthalocyanines Phthalocyanines are macrocyclic compounds that do not exist in nature but were accidentally discovered in laboratories as a by-product in 1907 [2] and as a copper salt in 1927 [3]. In the 1930s phthalocyanines became very interesting for industrial use as dye. Their colours are strong, bright blue to green and do not fade in sunlight. In the last two decades they even became important commercially as photoreceptor in laser beam printers and photocopiers.[4] Pc’s are used in fuel cells, solar cells, radiation sensors, electronic components and in medicine e.g. in cancer therapy [5][6][7][8][9]. Although the molecular structure of metal-free and metal phthalocyanines was soon discovered (1934) [10] there are still ongoing investigations about the single-crystal and solid- state structure of phthalocyanine molecular films for relating it to the many physical properties characteristic for each application. Figure 2-1: Metal phthalocyanine (left), metal porphyrin ring and a pyrrole group Phthalocyanines have a porphyrin like structure. Porphyrin consists of four pyrrole units (C4H5N) linked by four methine bridges (-CH-). (See Figure 2-1). Phthalocyanine (C32H18N8Me) instead consists of four pyrrole units with four carbons attached in ring structure (benzene) linked together by N bridges3. In the centre of the ring structure one can find two H atoms (metal-free Pc) or a metal ion (metal Pc), usually a transition metal from the first transition series4 in the periodic system [11]. The bonds in the molecule are covalent bonds5. The central atom coordinates with the pyrrole nitrogen atoms. (See Figure 2-1). Phthalocyanines crystallize by forming stacks of molecules. The interaction between the molecule layers is weak, mediated by van der Waals forces.[12] 3 The nitrogen bridges are also called aza-bridges. Phthalocyanine is therefore sometimes called an azaporphyrin. 4 The transition metals of the first transition series are Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn 5 In a covalent bond atoms share one or more electron pairs. 5 3 Experimental set-up and technique The experimental technique used in this study is known as core level (CL) photoelectron spectroscopy (PES). It can deliver information about the chemical composition of a sample and for this reason PES is also called ESCA - Electron Spectroscopy for Chemical Analysis. ESCA is based on the information gained by photoelectrons emitted from the sample under x- ray excitation. This technique is also known as XPS (X-ray Photoelectron Spectroscopy). It was developed in the late 50’s at Uppsala University by K. Siegbahn and his group [13]. XPS is a surface sensitive method probing the energy levels of inner shell (=core) electrons. XPS does not only give us information on the chemical composition of a sample but probes even the oxidation states of the atoms in the sample and molecule-surface interactions between sample and carrier. 3.1 Principles